Mechanistic Insights into the Reaction of <i>N</i>‐Propargylated Pyrrole‐ and Indole‐Carbaldehyde with Ammonia, Alkyl Amines, and Branched Amines: A Synthetic and Theoretical Investigation

Sarı, Özlem; Seybek, Ali Fatih; Kaya, Serpil; Mengeş, Nurettin; Erdem, Safiye Sağ; Balcı, Metin

doi:10.1002/ejoc.201900084

Cited by 19 publications

(7 citation statements)

References 59 publications

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“…Initially, based on our previous works on the synthesis of azaheterocyclic compounds, [15] we chose N ‐propargyl‐C‐2‐substituted‐pyrroles as the starting material, synthesized as described in our previous report [16a–e] . Reaction of 13a with a base provided the indolizine derivative 15a in relatively good yield beside the allene 16 and the hydrolysis compound 17 .…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of Indolizines by Dimerization of N‐Propargylated Pyrroles via Allene Intermediates

et al. 2021

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Ten different N‐propargyl pyrrole derivatives having various substituents at the C‐2 position were synthesized. These derivatives were converted into indolizine derivatives by the [2+2] cycloaddition reaction of pyrrole N‐allene, forming in situ, by heating in PrOH in basic medium. The structures were characterized by NMR and X‐ray crystallography. The N‐propargylated derivatives smoothly underwent intermolecular cyclizations to produce indolizine derivatives in good yields. We proposed a radical mechanism for the dimerization. Reaction of an allene product with butylated hydroxytoluene (BHT), a radical scavenger, did not give any dimerization product. This result supports the radical reaction.

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Section: Resultsmentioning

confidence: 99%

“…[14] We have recently synthesized indolizine derivatives 14 by the reaction of N-propargylated pyrrole-carbaldehyde 13 with sterically bulky adamantylamine and t-butylamine (Scheme 2). [15] The development of general methods for the synthesis of indolizidines remains an area of active investigation.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Indolizines by Dimerization of N‐Propargylated Pyrroles via Allene Intermediates

et al. 2021

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“…Sodium hydride mediated Intramolecular heterocyclization in DMF between the substrate containing alkyne functionality and pyrrole nitrogen atom provided good yields of the required compounds [167] …”

Section: C−h Functionalization Of Pyrrolesmentioning

confidence: 99%

Recent Advances in Functionalization of Pyrroles and their Translational Potential

Hunjan

Panday

Gupta

et al. 2021

The Chemical Record

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Among the known aromatic nitrogen heterocycles, pyrrole represents a privileged aromatic heterocycle ranging its occurrence in the key component of “pigments of life” to biologically active natural products to active pharmaceuticals. Pyrrole being an electron‐rich heteroaromatic compound, its predominant functionalization is legendary to aromatic electrophilic substitution reactions. Although a few excellent reviews on the functionalization of pyrroles including the reports by Baltazzi in 1963, Casiraghi and Rassu in 1995, and Banwell in 2006 are available, they are fragmentary and over fifteen years old, and do not cover the modern aspects of catalysis. A review covering a comprehensive package of direct functionalization on pyrroles via catalytic and non‐catalytic methods including their translational potential is described. Subsequent to statutory yet concise introduction, the classical functionalization on pyrroles using Lewis acids largely following an ionic mechanism is discussed. The subsequent discussion follows the various metal‐catalyzed C−H functionalization on pyrroles, which are otherwise difficult to implement by Lewis acids. A major emphasize is given on the radical based pyrrole functionalization under metal‐free oxidative conditions, which is otherwise poorly highlighted in the literature. Towards the end, the current development of pyrrole functionalization under photocatalyzed and electrochemical conditions is appended. Only a selected examples of substrates and important mechanisms are discussed for different methods highlighting their scopes and limitations. The aromatic nucleophillic substitution on pyrroles (being an electron‐rich heterocycle) happened to be the subject of recent investigations, which has also been covered accentuating their underlying conceptual development. Despite great achievements over the past several years in these areas, many challenges and problems are yet to be solved, which are all discussed in summary and outlook.

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“…It should be noted that it is also possible to access with low yields to N- substituted-3-methyl derivatives 78b–d by mixing N -propargyl-indole-2-carbaldehyde 77 in the presence of amines (MeNH 2 , BnNH 2 and hexNH 2 ) as nucleophiles and Cs 2 CO 3 as a base without the need of any metal. The mechanism of this cyclization was discussed in detail by the authors [ 48 ].…”

Section: Pyrazinoindol-1-ones B: Synthesis and Biological Propertiesmentioning

confidence: 99%

Synthesis and Biological Activities of Pyrazino[1,2-a]indole and Pyrazino[1,2-a]indol-1-one Derivatives

et al. 2021

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This review concerns the synthesis and biological activities of pyrazino[1,2-a]indoles and pyrazino[1,2-a]indol-1-ones reported since 1997 and the discovery of biological activity of pyrazinoindole derivatives. In the first part, we first presented the synthetic routes that have been reported from a methodological point of view to access the pyrazinoindole unit according to cyclization reactions using or not using metal catalysts. Then, syntheses and neuropsychiatric, auto-immune, anti-infectious and anti-cancer properties of pyrazinoindoles were detailed. In the second part, we first reported the main accesses to pyrazinoindol-1-one substrates according to Michael reactions, metal-catalyzed and metal-free cyclization reactions. The syntheses and anti-cancer, anti-infectious, anti-allergenic and neuropsychiatric properties of pyrazinoindolones were next described and discussed.

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Mechanistic Insights into the Reaction of N‐Propargylated Pyrrole‐ and Indole‐Carbaldehyde with Ammonia, Alkyl Amines, and Branched Amines: A Synthetic and Theoretical Investigation

Cited by 19 publications

References 59 publications

Synthesis of Indolizines by Dimerization of N‐Propargylated Pyrroles via Allene Intermediates

Synthesis of Indolizines by Dimerization of N‐Propargylated Pyrroles via Allene Intermediates

Recent Advances in Functionalization of Pyrroles and their Translational Potential

Synthesis and Biological Activities of Pyrazino[1,2-a]indole and Pyrazino[1,2-a]indol-1-one Derivatives

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